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| United States Patent |
6,106,597
|
|
Starks
, et al.
|
August 22, 2000
|
Wax compositions comprising fatty ester poly(oxyalkylenated) colorants
Abstract
This invention relates to wax formulations comprised of specific
poly(oxyalkylenated) colorants having fatty ester terminal groups.
Preferably the wax formulation is a candle. Such polymeric ester capped
colorants provide excellent coloring, decreased migratory properties, and
improved balanced burning characteristics over traditional candle
colorants and dyestuffs. This invention also concerns methods of making
the aforementioned colored candle formulations as well as other colored
wax articles, such as crayons.
| Inventors:
|
Starks; Leonard J. (Duncan, SC);
Stephenson; E. Kyle (Spartanburg, SC);
Mahaffey, Jr.; Robert L. (Spartanburg, SC)
|
| Assignee:
|
Milliken & Company (Spartanburg, SC)
|
| Appl. No.:
|
216784 |
| Filed:
|
December 18, 1998 |
| Current U.S. Class: |
106/31.08; 44/275; 106/272 |
| Intern'l Class: |
C09D 013/00; C09D 191/06; C09D 191/08; C11C 005/00 |
| Field of Search: |
106/272,31.08
44/275
|
References Cited
U.S. Patent Documents
| 2392158 | Jan., 1946 | Lacey et al. | 260/169.
|
| 3344098 | Sep., 1967 | Horiguchi et al. | 260/22.
|
| 3734857 | May., 1973 | Moiso et al. | 252/51.
|
| 4167510 | Sep., 1979 | Brendle | 260/174.
|
| 4342683 | Aug., 1982 | Reel et al. | 260/156.
|
| 4602916 | Jul., 1986 | Wilson | 8/580.
|
| 4722738 | Feb., 1988 | Wilson | 8/527.
|
| 4732570 | Mar., 1988 | Baumgartner et al. | 8/506.
|
| 4871371 | Oct., 1989 | Harris | 8/403.
|
| 5084099 | Jan., 1992 | Jaeger et al. | 106/22.
|
| 5145573 | Sep., 1992 | Riedel et al. | 208/14.
|
| 5310887 | May., 1994 | Moore et al. | 534/729.
|
| 5621022 | Apr., 1997 | Jaeger et al. | 523/161.
|
| 5938828 | Aug., 1999 | Zhao et al. | 106/31.
|
Primary Examiner: Brunsman; David
Attorney, Agent or Firm: Moyer; Terry T., Parks; William S.
Claims
What is claimed is:
1. A colored wax composition comprising
a wax; and
a colorant defined by Formula (I)
R{A[(B).sub.n R.sup.1 ].sub.m }.sub.x (I)
wherein
R is an organic chromophore;
A is a linking moiety in said chromophore selected from the group
consisting of N, O, S, SO.sub.2 N, and CO.sub.2 ;
B is selected from the group of one or more alkyleneoxy constituents
containing from 2 to 4 carbon atoms;
n is an integer of from 2 to about 100;
m is 1 when A is O, S, or CO.sub.2, and m is 2 when A is N or SO.sub.2 N;
x is an integer of from 1 to about 5; and
R.sup.1 is a C.sub.8 to about C.sub.20 fatty acid moiety;
wherein the colorant is optionally diluted in a diluent surfactant.
2. The wax composition in claim 1 wherein
said wax is selected from the group consisting of mineral waxes, animal
waxes, vegetable waxes, synthetic waxes, and any mixtures thereof.
3. The wax composition in claim 2 wherein
said wax is selected from the group consisting of paraffin wax, montan wax,
ozokerite wax, microcrystalline wax, earth wax, beeswax, waspwax,
Chinesewax (insectwax), carnauba wax, sugarcane wax, candelilla wax, flax
wax, Fischer-Tropsch wax, polyethylene wax, and any mixtures thereof.
4. The wax composition in claim 3 wherein
said wax is paraffin wax.
5. The wax composition in claim 1 wherein
R is selected from the group consisting of azo, diazo, disazo, trisazo,
diphenylmethane, triphenylmethane, xanthene, nitro, nitroso, acridine,
methine, styryl, indamine, thiazole, oxazine, anthraquinone, and any
mixtures thereof;
B comprises a mixture of ethyleneoxy and propyleneoxy groups;
n is from about 4 to about 30;
x is 2; and
R.sup.1 is from C.sub.12 to C.sub.8 fatty acid.
6. The wax composition in claim 5 wherein
R is selected from the group consisting of azo, triphenylmethane, nitro,
methine, thiazole, and any mixtures thereof;
B comprises from about 0 to about 50% moles of ethyleneoxy groups and from
about 50 to about 100% moles of propyleneoxy groups;
n is from about 8 to about 20; and
R.sup.1 is from C.sub.14 to C.sub.18 fatty acid.
7. The wax composition in claim 6 wherein
B comprises from about 0 to about 40% moles of ethyleneoxy groups and from
about 60 to about 100% moles of propyleneoxy groups; and
R.sup.1 is C.sub.8 fatty acid.
8. The wax composition in claim 7 wherein B comprises 100% moles of
propyleneoxy groups.
9. A method of producing a colored wax article comprising the sequential
steps of
(a) providing a solution of molten wax;
(b) introducing into said molten wax a colorant defined by Formula (I)
R{A[(B).sub.n R.sup.1 ].sub.m }.sub.x (I)
wherein
R is an organic chromophore;
A is a linking moiety in said chromophore selected from the group
consisting of N, O, S, SO.sub.2 N, and CO.sub.2 ;
B is selected from the group of one or more alkyleneoxy constituents
containing from 2 to 4 carbon atoms;
n is an integer of from 2 to about 100;
m is 1 when A is O, S, or CO.sub.2, and m is 2 when A is N or SO.sub.2 N;
x is an integer of from 1 to about 5; and
R.sup.1 is a C.sub.8 to about C.sub.20 fatty acid moiety,
to produce a colored wax composition;
(c) pouring said colored wax composition into a mold; and
(d) allowing sufficient time for said colored wax composition to cool
within said mold.
10. The method of claim 9 wherein
said wax is selected from the group consisting of mineral waxes, animal
waxes, vegetable waxes, synthetic waxes, and any mixtures thereof.
11. The method of claim 10 wherein
said wax is selected from the group consisting of paraffin wax, montan wax,
ozokerite wax, microcrystalline wax, earth wax, beeswax, waspwax,
Chinesewax (insectwax), camauba wax, sugarcane wax, candelilla wax, flax
wax, Fischer-Tropsch wax, and any mixtures thereof.
12. The method of claim 11 wherein
said wax is paraffin wax.
13. The method of claim 9 wherein
R is selected from the group consisting of azo, diazo, disazo, trisazo,
diphenylmethane, triphenylmethane, xanthene, nitro, nitroso, acridine,
methine, styryl, indamine, thiazole, oxazine, anthraquinone, and any
mixtures thereof;
B comprises a mixture of ethyleneoxy and propyleneoxy groups;
n is from about 4 to about 30;
x is 2; and
R.sup.1 is from C.sub.12 to C.sub.18 fatty acid.
14. The method of claim 13 wherein
R is selected from the group consisting of azo, triphenylmethane, nitro,
thiazole, and any mixtures thereof;
B comprises from about 0 to about 50% moles of ethyleneoxy groups and from
about 50 to about 100% propyleneoxy groups;
n is from about 8 to about 20; and
R.sup.1 is from C.sub.14 to C.sub.18 fatty acid.
15. The method of claim 14 wherein
B comprises from about 0 to about 40% moles of ethyleneoxy groups and from
about 60 to about 100% moles of propyleneoxy groups; and
R.sup.1 is C.sub.18 fatty acid.
16. The method of claim 15 wherein
B comprises 100% moles of propyleneoxy groups.
17. The method of claim 15 wherein
said article is a candle.
18. The method of claim 15 wherein
said article is a crayon.
19. The method of claim 9 wherein
said article is a candle.
20. The method of claim 9 wherein
said article is a crayon.
Description
FIELD OF THE INVENTION
This invention relates to wax formulations comprised of specific
poly(oxyalkylenated) colorants having fatty ester terminal groups.
Preferably the wax formulation is a candle. Such polymeric ester capped
colorants provide excellent coloring, decreased migratory properties, and
improved balanced burning characteristics over traditional candle
colorants and dyestuffs. This invention also concerns methods of making
the aforementioned colored candle formulations as well as other colored
wax articles, such as crayons.
BACKGROUND OF THE PRIOR ART
All of the patents cited throughout this specification are hereby entirely
incorporated herein.
Historically, solvent dyes have been utilized as colorants within waxes,
particularly candles. Although these dyes provide good coloring throughout
the wax medium, solvent dyes are difficult to handle (powder or dust
form), easily stain a myriad of substrates (including a colorist's skin),
migrate out of hardened wax to discolor its storage wrapper or its
handler's skin, clog burning candle wicks with solid particulate dye, and
the like. It is therefore highly desirable to find effective alternatives
to such poorly performing wax dyes. There exists a need then to produce a
dye which provides effective, thorough, and homogeneous colorations to
wax, is easy to handle, will not migrate out of hardened wax, and will not
clog a candle wick with solid particles.
It has been found that the utilization of ester capped polyoxyalkylene
colorants provide all of the requisite beneficial properties outlined
above which are desirable within wax compositions, particularly within
candles. Such colorants are present in a neat liquid state at 25.degree.
C. which thus facilitates handling and substantially eliminates any wick
clogging problems. Furthermore, such colorants are extremely stable when
dispersed within a hardened wax medium and therefore cannot migrate out of
solution. Also, an additive, such as stearic acid, may be introduced
within such wax compositions in order to produce a crayon composition
which exhibits the same types of beneficial properties as outlined above
for candles, except for the non-clogging characteristics of a wick.
Ester capped polyoxyalkylene colorants are known as fugitive tints for
certain textiles, in particular to color code threads during production
and/or finishing operations. For example, U.S. Pat. No. 4,167,510, to
Brendle discloses the same ester capped colorants as used in the present
candle compositions but for use in textile and thread tinting
applications. Patentee does not discuss nor allude to any other coloring
methods other than textiles for his ester capped colorants. Other possible
esterified colorants have been taught within U.S. Pat. No. 4,871,371, to
Harris; however, these colorants are utilized solely for the purpose of
coloring aqueous or non-aqueous liquids, not waxes, and do not require a
fatty acid moiety. Patentee does disclose the addition of alkoxylated
fatty acids as diluents for his colorants, but makes no mention of a fatty
acid group on the colorant itself. Esterified polymeric colorants within
liquid petroleum or mineral oil compositions are taught within U.S. Pat.
No. 3,734,857, to Moiso et al., and U.S. Pat. No. 5,145,573, to Riedel et
al.; however, the possible esters within these references are limited to
short chain (C.sub.1 -C.sub.4) moieties. Therefore these patents neither
teach nor fairly suggest the specific candle compositions of the present
invention.
OBJECTS OF THE INVENTION
It is therefore an object of this invention to provide a non-staining,
non-migrating, non-wick-clogging liquid colorant for utilization within a
wax candle composition. A further objective of this invention is to
provide a candle which is produced through the utilization of a liquid
colorant without the need for volatile organic solvents (such as xylene,
toluene, and the like). Still another object of the invention is to
produce a colored wax composition which will not stain a handler's skin or
discolor its storage wrapper.
SUMMARY OF THE INVENTION
The present invention is thus a colored wax composition comprising
polyoxyalkylenated fatty acid-ester capped colorants. The term wax is
intended to encompass any wax or wax-like substance in which unmodified
reactive dyes are substantially insoluble. Waxes are generally defined as
compositions comprising saturated fatty (high molecular weight)
hydrocarbons. As will be well understood and appreciated by one of
ordinary skill in this art, the term wax is not limited to compositions
comprising only such saturated fatty (high molecular weight) hydrocarbons
as myriad additives, such as plasticizers and the like, and impurities,
including naturally produced and occurring impurities, are also present in
various proportions within wax or wax-like compositions, particularly
within candle and crayon formulations. More specific types of such waxes
include mineral waxes, such as paraffin, montan, ozokerite,
microcrystalline wax, earth wax, and the like; animal waxes, such as
beeswax, waspwax, Chinesewax (insectwax), and the like; vegetable waxes,
such as camauba, sugarcane wax, candelilla, flax wax, and the like; and
synthetic waxes, such as Fischer-Tropsch wax, polyethylene wax, and the
like. Such waxes generally melt at temperatures ranging from about 50 to
about 70.degree. C. For instance, paraffin wax, which is the most
prevalent and most versatile type of wax, melts in a range of between
about 55 and about 65.degree. C. Other types of waxes (called additive
waxes) may be added to candle and/or crayon compositions to produce
differing effects (such as color variations, for example) and may alter
the melting point of the base wax composition to a certain degree. The
particular wax articles encompassed within this invention solid wax
implements, such as candles, crayons, ear plugs, and the like.
Accordingly, this invention includes a wax composition comprising
a wax; and
a colorant defined by Formula (I)
R{A--[(B).sub.n R.sup.1 ].sub.m }.sub.x (I)
wherein
R is an organic chromophore;
A is a linking moiety in said chromophore selected from the group
consisting essentially of N, O, S, SO.sub.2 N, or CO.sub.2 ;
B is selected from one or more alkyleneoxy constituents containing from 2
to 4 carbon atoms;
n is an integer of from 2 to about 100;
m is 1 when A is O, S, or CO.sub.2, and m is 2 when A is N or SO.sub.2 N;
x is an integer of from 1 to about 5; and
R.sup.1 is a C.sub.8 to about C.sub.20 fatty acid moiety.
The organic chromophore is, more specifically, one or more of the following
types of compounds: azo, diazo, disazo, trisazo, diphenylmethane,
triphenylmethane, xanthene, nitro, nitroso, acridine, methine, styryl,
indamine, thiazole, oxazine, or anthraquinone. Preferably, R is one or
more of azo, diazo, triphenylmethane, methine, or thiazole based
compounds. Group A is present on group R and is utilized to attach the
polyoxyalkylene constituent to the organic chromophore. Nitrogen is the
preferred linking moiety. The polyoxyalkylene group is generally a
combination of ethylene oxide and propylene oxide monomers. Preferably
propylene oxide is present in the major amount, and most preferably the
entire polyoxyalkylene constituent is propylene oxide.
The preferred number of moles (n) of polyoxyalkylene constituent per
ester-capped chain is from 2 to 15, more preferably from 4 to 10. Also,
preferably two such ester capped chains are present on each polymeric
colorant compound (x, above, is preferably 2). In actuality, the number of
moles (n) per ester-capped chain is an average of the total number present
since it is very difficult to control the addition of specific numbers of
moles of alkyleneoxy groups. Furthermore, the preferred fatty acid chain
length is from C.sub.12 -C.sub.18 ; more preferably from C.sub.14 to
C.sub.18 ; and most preferably C.sub.18.
The amount of colorant added depends largely on the intended end use. For
example, if the colored wax composition is a crayon, the colorant is
generally added in an amount from about 0.01 to about 15% by weight of the
total wax composition in order to introduce sufficient colorant not only
to color the wax composition, but also to effectuate a proper transfer of
the colorant to a writing surface. Preferably, the required amount is from
about 0.1 to about 12% by weight; more preferably from about 1 to about
12%; and most preferably from about 5 to about 10.5%. If the wax
composition is a candle, as merely an example, the amount of colorant
added is generally from about 0.001 to about 35 by weight of the total wax
composition; preferably from about 0.01 to about 2%; more preferably from
about 0.01 to about 1.0%; and most preferably from about 0.01 to about
0.1%.
The invention also encompasses a method of producing a colored wax article
comprising the sequential steps of
(a) providing a solution of molten wax;
(b) introducing into said molten wax a colorant defined by Formula (I)
R{A[(B).sub.n R.sup.1 ].sub.m }.sub.x (I)
wherein
R is an organic chromophore;
A is a linking moiety in said chromophore selected from the group
consisting essentially of N, O, S, SO.sub.2 N, and CO.sub.2 ;
B is selected from one or more alkyleneoxy constituents containing from 2
to 4 carbon atoms;
n is an integer of from 2 to about 100;
m is 1 when A is O, S, or CO.sub.2, and m is 2 when A is N or SO.sub.2 N;
x is an integer of from 1 to about 5; and
R.sub.1 is a C.sub.8 to about C.sub.20 fatty acid moiety,
thereby producing a colored wax composition;
(c) pouring said colored wax composition into a mold; and
(d) allowing sufficient time for said colored wax composition to cool
within said mold.
The preferred article to be manufactured in this inventive process is a
candle; however, as noted above, crayons, ear plugs, and the like, may
also be produced by this method.
Any other standard wax composition additives, such as fatty acids, resins,
preservatives, wax colorants other than the currently utilized ester
capped polymeric colorants, pigments, surfactants, and antistatic
compounds may be incorporated within the inventive wax composition or
utilized within the inventive production method. Of particular interest is
the utilization of a diluent surfactant, for example mineral oil or a
substituted or unsubstituted sorbitan monoester, such as sorbitan
monooleate (Span.RTM. 80, from Imperial Chemical) and/or ethoxylated
sorbitan monooleate (such as Tween.RTM. 80, also available from Imperial
Chemical). Such diluent surfactants provide improvements in incorporating
the fatty ester polymeric polyoxyalkylenated colorants within the target
wax compositions. As above, the amount of surfactant added will depend
primarily on the amount of colorant added and thus is highly dependent on
the intended end use of the colored wax composition. For instance, where
such a diluent surfactant is utilized to color a wax candle composition,
the surfactant is generally present in a range ot ratios of colorant to
surfactant from about 1:1 to about 1:10. Preferably, this ratio is from
about 1:1.5 to about 1:7.5; more preferably, from about 1:2 to about 1:5;
and most preferably from about 1:2.5 to about 1:3.25.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Without limiting the scope of the invention, the preferred features of the
invention are exemplified below.
The preferred esterified colorants are listed below in tabular form and in
correlation with Formula (I) listed above (EO is ethyleneoxy and PO is
propyleneoxy).
TABLE
______________________________________
Preferred Poly(oxyalkylenated) Colorants
Col. B
# R A (with moles)
R.sup.1
n m x
______________________________________
1 Methine N 1EO; 5PO;
C.sub.18
9 2 1
3EO
2 Benzothiazole
N 1EO; 5PO;
C.sub.18
9 2 1
3EO
3 Triphenylmethane
N 1EO; 5PO;
C.sub.18
9 2 2
3EO
4 Benzothiazole
N 3PO C.sub.18
3 2 1
5 Triphenylmethane
N 3PO C.sub.18
3 2 2
6 Methine N 1EO; 7.5PO;
C.sub.18
11 2 1
2.5EO
7 Triphenylmethane
N 1EO; 6.5PO
C.sub.18
7.5 2 2
______________________________________
Production of Esterified Colorants
Initially, the preferred colorants for use in the inventive candle
compositions are produced as follows in two separate types of procedures:
A. Esterification of Colorants
EXAMPLE 1
100.00 g of Colorant 1, above, but with an hydrogen in place of the
C.sub.18 fatty acid group of R.sup.1, were charged to a reactor with 15.92
triethylamine and 20 mL of tetrahydrofuran (THF). To this mixture were
slowly added 47.77 g of stearoyl chloride at room temperature. The
resulting mixture was then heated to 40.degree. C. and monitored by
infrared (IR) spectroscopy to determine the point in time during the
reaction at which the acid chloride peak (1800 nm) disappeared. The
mixture was then placed in a separatory funnel in which it was washed with
sodium carbonate and water. The organic phase of the separated mixture was
then filtered and stripped under vacuum to yield 83.36 g of a yellow
liquid polymeric colorant in accordance with Colorant 1 of the TABLE.
EXAMPLE 2
100.00 g of Colorant 2, above, but with an hydrogen in place of the
C.sub.18 fatty acid group of R.sup.1, were charged to a reactor with 18.15
triethylamine and 20 mL of tetrahydrofuran (THF). To this mixture were
slowly added 81.67 g of stearoyl chloride at room temperature. The
resulting mixture was then heated to 40.degree. C. and monitored by
infrared (IR) spectroscopy to determine the point in time during the
reaction at which the acid chloride peak (1800 cm.sup.-1) disappeared. The
mixture was then placed in a separatory funnel in which it was washed with
sodium carbonate and water. The organic phase of the separated mixture was
then filtered and stripped under vacuum to yield 150.73 g of a red liquid
polymeric colorant in accordance with Colorant 2 of the TABLE.
EXAMPLE 3
100.00 g of Colorant 3, above, but with an hydrogen in place of the
C.sub.18 fatty acid group of R.sup.1 were charged to a reactor with 21.82
triethylamine and 20 mL of tetrahydrofuran (THF). To this mixture were
slowly added 98.18 g of stearoyl chloride at room temperature. The
resulting mixture was then heated to 40.degree. C. and monitored by
infrared (IR) spectroscopy to determine the point in time during the
reaction at which the acid chloride peak (1800 cm.sup.-1) disappeared. The
mixture was then placed in a separatory funnel in which it was washed with
sodium carbonate and water. The organic phase of the separated mixture was
then filtered and stripped under vacuum to yield 181.93 g of a blue liquid
polymeric colorant in accordance with Colorant 3 of the TABLE.
B. Formation of Colorants After Esterification of Intermediates
EXAMPLE 4
An esterified intermediate was produced by the following method. 84 g of an
aniline adduct containing 6 moles of PO was reacted with 110 g of
isostearic acid and 2 g of hypophosphorous acid. The resulting mixture was
heated to 200.degree. C. for about 15 hours and produced 126.63 g of the
compound of formula (I):
##STR1##
EXAMPLE 5
An esterified polymeric colorant was then formed by the following method.
75 g of phosphoric acid (85%) was added to 10 g of sulfuric acid (70%). To
this mixture was slowly added 13.9 g of 2-amino-4-methyl benzothiazole.
This coupler mixture was cooled to 0-5.degree. C. for 1 hour, after which
2.9 g of sodium nitrite was then added. A separate solution containing
29.67 g of the propoxylated (6PO) aniline isostearate intermediate of
EXAMPLE 4 was then dissolved in 200 g of water with stirring. The coupler
mixture was then added to the intermediate and stirred for one hour at
room temperature. The pH of the resulting mixture was then adjusted to 7.0
(caustic soda was utilized) and the mixture was then allowed to separate
into distinct phases in a 60.degree. C. oven. The resulting organic phase
was filtered and stripped under vacuum to yield 69.54 g of a red liquid
polymeric colorant as defined by the formula of Colorant 4 in the TABLE,
above.
EXAMPLE 6
A different esterified colorant was prepared by the following method. 50.67
g of the propoxylated (6PO) aniline isostearate intermediate of EXAMPLE 4,
7.46 g of ortho-formyl benzenesulfonic acid, sodium salt (OFBSA), 0.76 g
of urea, 0.02 g of ammonium meta vanadate (catalyst), and 1.59 g of water
were all charged to a reactor with stirring and heated to about
95-100.degree. C. To this mixture was slowly added, by addition funnel, a
separate solution containing 2.51 g of hydrogen peroxide (35%) and 7.1 g
of water. This new mixture was then allowed to react for 30 minutes.
Subsequently, the reacted mixture was placed in a separatory funnel and
phase separated in a 60.degree. C. oven. The resultant organic phase was
filtered and stripped under vacuum to yield 38.42 g of a blue liquid
polymeric colorant as defined by the formula for Colorant 5 in the TABLE,
above.
Introduction of Colorants into Candle (or Crayon) Compositions
This process generally entailed adding the colorant (or blend of colorants)
to molten wax and stirring (while the solution remained in a molten state)
until the wax solution became an homogeneously colored formulation. This
liquid wax solution was allowed to cool in a candle mold surrounding a
wick, whereupon the wax eventually formed a colored solid candle.
Colorants 1 through 3 from the TABLE, above, above, were cut to an
absorptivity of about 5.0 in wax through dilution with a sorbitan
monooleate diluent surfactant (such as Span.RTM. 80, available from
Imperial Chemical) prior to their introduction within the molten wax
media. Colorants 5 through 7, above, were added directly to the molten
waxes at an absorptivity of about 0.1 without the addition of a diluent
surfactant.
EXAMPLE 7
0.44 g of the Colorant from EXAMPLE 1 (Colorant 1 from the TABLE, above)
were diluted in 1.36 g of Span.RTM. 80 and subsequently introduced within
900 g of molten paraffin wax. After mixing, the liquid wax solution became
a homogeneous yellow composition. The liquid was then poured into a candle
mold with a wick inserted in the middle and subsequently allowed to cool.
The resultant homogeneous liquid wax (prior to cooling) exhibited little
or no colorant droplets and the colorant was well dispersed throughout the
resultant solid wax candle (after cooling). Furthermore, after a storage
time of 28 days within a polyethylene wrapper at 25.degree. C., the
colorant remained homogeneously dispersed throughout the candle.
Additionally, after this storage period, no staining of the wrapper was
detected thus indicating no appreciable migration of the colorant from the
solid wax medium.
EXAMPLE 8
0.55 g of the Colorant from EXAMPLE 2 (Colorant 2 from the TABLE, above)
were diluted in 1.25 g of Span.RTM. 80 and subsequently introduced within
900 g of molten paraffin wax. After mixing, the liquid wax solution became
a homogeneous red composition. The liquid was then poured into a candle
mold with a wick inserted in the middle and subsequently allowed to cool.
The resultant homogeneous liquid wax (prior to cooling) exhibited little
or no colorant droplets and the colorant was well dispersed throughout the
resultant solid wax candle (after cooling). Furthermore, after a storage
time of 28 days within a polyethylene wrapper at 25.degree. C., the
colorant remained homogeneously dispersed throughout the candle.
Additionally, after this storage period, no staining of the wrapper was
detected thus indicating no appreciable migration of the colorant from the
solid wax medium.
EXAMPLE 9
0.44 g of the Colorant from EXAMPLE 3 (Colorant 3 from the TABLE, above)
were diluted in 1.36 g of Span.RTM. 80 and subsequently introduced within
900 g of molten paraffin wax. After mixing, the liquid wax solution became
a homogeneous blue composition. The liquid was then poured into a candle
mold with a wick inserted in the middle and subsequently allowed to cool.
The resultant homogeneous liquid wax (prior to cooling) exhibited little
or no colorant droplets and the colorant was well dispersed throughout the
resultant solid wax candle (after cooling). Furthermore, after a storage
time of 28 days within a polyethylene wrapper at 25.degree. C., the
colorant remained homogeneously dispersed throughout the candle.
Additionally, after this storage period, no staining of the wrapper was
detected thus indicating no appreciable migration of the colorant from the
solid wax medium.
EXAMPLE 10
0.55 grams of the Colorant of EXAMPLE 5 (Colorant 4 of the TABLE, above)
were introduced within 900 grams of molten paraffin wax. After mixing, the
liquid wax solution became an homogeneous red composition. The liquid was
then poured into a candle mold with a wick inserted in the middle and was
then allowed to cool. The homogeneous liquid had little or no colorant
droplets and the colorants were well dispersed in the resultant solid wax
candle. Furthermore, after a storage time of 28 days within a polyethylene
wrapper at 25.degree. C., the colorant remained homogeneously dispersed
throughout the candle. Additionally, after this storage period, no
staining of the wrapper was detected thus indicating no appreciable
migration of the colorant from the solid wax medium.
EXAMPLE 11
0.37 grams of the Colorant of EXAMPLE 6 (Colorant 5 from the TABLE, above)
were introduced within 900 grams of molten paraffin wax. After mixing, the
liquid wax solution became an homogeneous blue composition. The liquid was
then poured into a candle mold with a wick inserted in the middle and was
then allowed to cool. The homogeneous liquid had little or no colorant
droplets and the colorants were well dispersed in the resultant solid wax
candle. Furthermore, after a storage time of 28 days within a polyethylene
wrapper at 25.degree. C., the colorant remained homogeneously dispersed
throughout the candle. Additionally, after this storage period, no
staining of the wrapper was detected thus indicating no appreciable
migration of the colorant from the solid wax medium.
EXAMPLE 12
3.0 grams of Colorant 6 of the TABLE, above, were introduced into 33.7
grams of molten paraffin wax. After mixing, the liquid wax solution became
an homogeneous yellow composition. The liquid was then poured into a
crayon mold and allowed to cool. The homogeneous liquid had little or no
colorant droplets and the colorant was well dispersed within the resultant
solid wax crayon. Furthermore, the crayon exhibited very good transfer to
a paper writing surface.
EXAMPLE 13
3.2 grams of Colorant 7 of the TABLE were introduced into 32.3 grams of
molten paraffin wax. After mixing, the liquid wax solution became an
homogeneous blue composition. The liquid was then poured into a crayon
mold and allowed to cool. The homogeneous liquid had little or no colorant
droplets and the colorant was well dispersed within the resultant solid
wax crayon. Furthermore, the crayon exhibited very good transfer to a
paper writing surface.
C. Comparative Examples
Formation of Comparative Non-esterified Intermediate
EXAMPLE 14
Comparative
A comparative non-esterified intermediate was formed by the following
method. 1392 g of PO was bubbled into a reactor containing 724 g of
N,N-dihydroxyethylaniline and 24 g of flake KOH at 250.degree. C. and 5
psi until 6 molar equivalents of PO were absorbed. The resulting product
is represented by formula (II):
##STR2##
Formation of Non-esterified Polymeric Colorants
EXAMPLE 15
Comparative
A comparative non-esterified polymeric colorant was produced by the
following method. 75 g of phosphoric acid (85%) was added to 10 g of
sulfuric acid (70%). To this mixture was slowly added 13.9 g of
2-amino-4-methyl benzothiazole. This coupler mixture was cooled to
0-5.degree. C. for 1 hour, after which 2.9 g of sodium nitrite was then
added. A separate solution containing 29.67 g of the propoxylated (6PO)
aniline intermediate of EXAMPLE 14 was then dissolved in 200 g of water
with stirring. The coupler mixture was then added to the intermediate and
stirred for one hour at room temperature. The pH of the resulting mixture
was then adjusted to 7.0 (caustic soda was utilized) and the mixture was
then allowed to separate into distinct phases in a 60.degree. C. oven. The
resulting organic phase was filtered and stripped under vacuum to yield a
red liquid non-esterified polymeric colorant.
EXAMPLE 16
Comparative
A different non-esterified polymeric colorant was prepared by the following
method. 50.67 g of the propoxylated (6PO) aniline intermediate of EXAMPLE
14, 7.46 g of OFBSA, 0.76 g of urea, 0.02 g of ammonium meta vanadate
(catalyst), and 1.59 g of water were all charged to a reactor with
stirring and heated to about 95-100.degree. C. for 1 hour. To this mixture
was slowly added, by addition funnel, a separate solution containing 2.51
g of hydrogen peroxide (35%) and 7.1 g of water. This new mixture was then
allowed to react for 30 minutes. Subsequently, the reacted mixture was
placed in a separatory funnel and phase separated in a 60.degree. C. oven.
The resultant organic phase was filtered and stripped under vacuum to
yield a blue liquid non-esterified polymeric colorant.
Introduction of Comparative Colorants within Candle (or Cravon)
Compositions
EXAMPLE 17
Comparative
0.27 grams of the comparative Colorant of EXAMPLE 15 were introduced into
900 grams of molten paraffin wax. After mixing, the liquid wax solution
became an heterogeneous red composition. The liquid was then poured into a
candle mold with a wick inserted in the middle and was then allowed to
cool. The homogeneous liquid had large colorant droplets and the colorants
were poorly dispersed in the solid wax candle with the majority of the
colorant in the bottom. Furthermore, the colorants also began migrating
from the outer walls of the wax candle into its polyethylene wrapper upon
contact. After a storage period of 28 days at 25.degree. C., the wrapper
was examined further and found to be thoroughly colored while the wax
candle exhibited undesirable color variations throughout.
EXAMPLE 18
Comparative
0.20 grams of the Colorant 6 of the TABLE, above, but with the replacement
of the R.sup.1 group with an hydrogen, were introduced into 900 grams of
molten paraffin wax. After mixing, the liquid wax solution became an
heterogeneous blue composition. The liquid was then poured into a candle
mold with a wick inserted in the middle and was then allowed to cool. The
homogeneous liquid had large colorant droplets and the colorants were
poorly dispersed in the solid wax candle with the majority of the colorant
in the bottom. Furthermore, the colorants also began migrating from the
outer walls of the wax candle into its polyethylene wrapper upon contact.
After a storage period of 28 days at 25.degree. C., the wrapper was
examined further and found to be thoroughly colored while the wax candle
exhibited undesirable color variations throughout.
EXAMPLE 19
Comparative
2.2 grams of Colorant 6 of the TABLE, above, but with the replacement of
the R.sup.1 group with an hydrogen, were introduced into 35.2 grams of
molten paraffin wax. After mixing, the liquid wax solution became an
heterogeneous yellow composition. The liquid was then poured into a crayon
mold and allowed to cool. The heterogeneous liquid contained colorant
droplets and the colorant was not well dispersed within the resultant
solid wax crayon. The crayon also exhibited a poor, uneven transfer of
color to a paper writing surface.
EXAMPLE 20
Comparative
2.6 grams of Colorant 6 of the TABLE, above, but with the replacement of
the R.sup.1 group with an hydrogen, and 1.3 grams of Span.RTM. 80 were
introduced into 39.2 grams of molten paraffin wax. After mixing, the
liquid wax solution became an heterogeneous yellow composition. The liquid
was then poured into a crayon mold and allowed to cool. The heterogeneous
liquid contained colorant droplets and the colorant was not well dispersed
within the resultant solid wax crayon. The crayon also exhibited a poor,
uneven transfer of color to a paper writing surface.
EXAMPLE 21
Comparative
2.1 grams of Colorant 7 of the TABLE, above, but with the replacement of
the R.sup.1 group with an hydrogen, were introduced into 32.7 grams of
molten paraffin wax. After mixing, the liquid wax solution became an
heterogeneous blue composition. The liquid was then poured into a crayon
mold and allowed to cool. The heterogeneous liquid contained colorant
droplets and the colorant was not well dispersed within the resultant
solid wax crayon. The crayon also exhibited a poor, uneven transfer of
color to a paper writing surface.
EXAMPLE 22
Comparative
2.5 grams of Colorant 7 of the TABLE, above, but with the replacement of
the R.sup.1 group with an hydrogen, and 1.25 grams of Span(t 80 were
introduced into 38.4 grams of molten paraffin wax. After mixing, the
liquid wax solution became an heterogeneous yellow composition. The liquid
was then poured into a crayon mold and allowed to cool. The heterogeneous
liquid contained colorant droplets and the colorant was not well dispersed
within the resultant solid wax crayon. The crayon also exhibited a poor,
uneven transfer of color to a paper writing surface.
As these results indicate, the ester-capped polyoxyalkylenated polymeric
colorants provide superior performance in wax compositions than the
non-esterified colorants.
While specific features of the invention have been described, it will be
understood, of course, that the invention is not limited to any particular
configuration or practice since modification may well be made and other
embodiments of the principals of the invention will no doubt occur to
those skilled in the art to which the invention pertains. Therefore, it is
contemplated by the appended claims to cover any such modifications as
incorporate the features of the invention within the true meaning, spirit,
and scope of such claims.
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